Method of combining crystalline sugar with impregnating agents and products produced thereby

ABSTRACT

Massecuite Aggregated Microcrystalline Sugar granules (structurally comprising cohered sugar microcrystals with internal capillary networks) are employed as a means to combine crystalline sugar with solid or liquid modifying agents which are dissolved (or otherwise dispersed) in an aqueous or organic solvent carrier, which is sprayed (or otherwise applied) onto a bed of the granules while they are being agitated and intermixed. The liquid carrier and modifying agent are absorbed into the granules to achieve internal impregnation thereof. Where the liquid carrier is relatively volatile compared to the modifying agent, as when the added substance is normally a solid, the carrier can be evaporated leaving the added substance within the granules. Either with or without removal (viz by evaporation or drying) of the liquid carrier, the impregnated granules can be subjected to a second treatment in which a pore closure material is applied to reduce the porosity of the surface layers of the granules, and thereby at least partially seal off the impregnated agent from escape to or contact with the atmosphere. Alternatively, the impregnated granules without drying and/or subjected to a second treatment can be packaged in sealed containers.

United States Patent 72] Inventors [2 1 1 Appl. No. [22] Filed [45]Patented [73] Assignee [54] METHOD OF COMBINING CRYSTALLINE SUGAR WITHIMPREGNATING AGENTS AND PRODUCTS PRODUCED THEREBY 15 Claims, No Drawings52 us. 01 127/30, 18/79, 99/78, 99/134 R, 99/140 R, 99/148 R, 99 010. 4,127/29, 127/63, 424/361 [51] Int. Cl C1311 l/00 [56] References CitedUNITED STATES PATENTS 1,902,773 3/1933 Hale 127/30 2,949,401 8/1960Wershaw 424/361 3,293,133 12/1966 Hill 424/361 3,347,682 10/1967Rosenstein 424/361 FOREIGN PATENTS 508,602 6/ l 955 Italy OTHERREFERENCES Assistant Examiner-Sidney Marantz Attorney-Dawson, Tilton,Fallon and Lungmus ABSTRACT: Massecuite Aggregated MicrocrystallineSugar granules (structurally comprising cohered sugar microcrystals withinternal capillary networks) are employed as a means to combinecrystalline sugar with solid or liquid modifying agents which aredissolved (or otherwise dispersed) in an aqueous or organic solventcarrier, which is sprayed (or otherwise applied) onto a bed of thegranules while they are being agitated and intermixed. The liquidcarrier and modifying agent are ab sorbed into the granules to achieveinternal impregnation thereof. Where the liquid carrier is relativelyvolatile compared to the modifying agent, as when the added substance isnormally a solid, the carrier can be evaporated leaving the addedsubstance within the granules. Either with or without removal (viz byevaporation or drying) of the liquid carrier, the impregnated granulescan be subjected to a second treatment in which a pore closure materialis applied to reduce the porosity of the surface layers of the granules,and thereby at least partially seal 011' the impregnated agent fromescape to or contact with the atmosphere. Alternatively, the impregnatedgranules without drying and/or subjected to a second treatment can bepackaged in sealed containers.

METHOD OF COMBINING CRYSTALLINE SUGAR WITH IMPREGNATING AGENTS ANDPRODUCTS PRODUCED THEREBY BACKGROUND In recent years, a new process hasbeen developed for preparing free-flowing sugar granules fromcrystallizable sugars. The process is particularly applicable to themanufacture of granular dextrose products from starch hydrolysates ofhigh D.E., which are referred to as Total Sugar" products, since theyare composed of dextrose in admixture with the residual oligosaccharidesof the saccharification. However, the process is also applicable tosucrose, and, in fact, to any other crystallizable sugar. The details ofthe process are set out in copending application Ser. No. 674,168, filedOct. 10, 1967, entitled Novel Granular Sugar Products and Process forProducing.

The process of the cited application has sometimes been referred to asSpray Crystallization." However, the product produced by the process canperhaps more accurately be described as Spray-Drier Aggregated" granules(herein after SDA" granules). The crystallization takes place primarilybefore and after the spray drying step. In addition to removing asubstantial quantity of water, one of the functions of the spray dryingis to form the basic aggregate structure, the granular aggregates thusobtained being subsequently aged and dried to complete the granulationprocess.

More specifically, in the process of the cited application, a watersolution of a crystallizable sugar is subjected to partialcrystallization to form a pumpable massecuite composed essentially ofmicrocrystals of sugar dispersed in a saturated water solution of sugar.This massecuite, which may contain from 40 to 60 percent of the sugar incrystalline form, is sprayed into a drying air stream to form atomizeddroplets and to remove part of the water from the droplets in the airstream to form granular aggregates of the microcrystals containingresidual crystallizable sugar solution. Essentially each droplet forms asingle aggregate of generally spherical shape. This step is preferablycarried out in a spray dryer tower where the massecuite droplets areformed at the top and fall downwardly through the tower with theevaporation of water therefrom. Where the hydrate crystal form iscritical, as with the conversion of dextrose to dextrose monohydratecrystals, the spray dryer is operated at a sufficiently low temperatureto avoid formation of anhydrous dextrose or other unstable crystalforms. For example, the massecuite droplets during spray drying of astarch hydrolysate can be kept below 50 C. With sucrose and othersugars, the spray drying temperature can be varied over a wider range,especially where the sugar has only one crystalline form, such as withsucrose which fonns only anhydrous crystals.

The granular crystalline material produced by the spray aggregationprocess just described, will contain additional crystallizable sugar,which may be in the form of a supersaturated solution that will rapidlycrystallize. However, the granules obtained from the spray dryer havesufficient structural integrity to permit them to be transferred toother processing apparatus for completion of the crystallization. Thisfurther processing can include an aging procedure in whichcrystallization is continued with or without removal of additionalwater. As a final step, however, it is desirable to subject the granularaggregates to drying to force completion of the crystallization, and atthe same time to reduce the free water content to a very low level.Where part of the water combines with the sugar as it crystallizes, freewater is eliminated in this way as well as by evaporation. The freewater content of the final granular products will usually be below 1percent by weight, and may be as low as 0.5 percent or lower. Where thegranular product is formed principally of dextrose monohydrate,overdrying can convert some of the monohydrate crystals to anhydrouscrystals, which may be undesirable unless a product comprising a mixtureof monohydrate and anhydrous crystals is desired.

it has been proposed to incorporate modifying agents, such as syntheticsweetening agents, edible organic acids, and food flavoring substancesin a spray drier aggregated sugar product by dispersing the modifyingagent or additive in the massecuite before spraying. The application ofthis procedure is limited, however, and it has certain inherentdisadvantages. Obviously, the additive cannot be of a kind or added insuch a quantity as to interfere with the completion of thecrystallization of the sugar during and after spray drying. An even moreserious disadvantage is that the additive will necessarily contaminatethe massecuite mixing, pumping, and spraying apparatus. Consequently,after producing a product containing a particular additive, it would benecessary to thoroughly clean all of the apparatus contacted with theadditive before resuming production of an unmodified crystallineproduct, or a product containing a different additive. Since forsatisfactory production operation, the spray drier apparatus must be ofvery large size and capacity, shutdown time for cleaning, even ifthorough cleaning can be made feasible, is highly objectionable andincreases overall operating costs in relation to volume of production.Another disadvantage of such an addition to the massecuite is that inthe extensive contact of each granule or aggregate with warm air, asnecessary to effect water removal in the spray tower, a significantamount of undesirable oxidation andlor loss of additive due tovolatilization may occur.

SUMMARY The present invention involves the discovery that the Spray--Drier Aggregated granules (or their equivalent as herein afterdescribed) have substantial internal free volume, comprising an internalcapillary network, which extends from the outer surfaces of the granulesinto the interior thereof, and that this permits a substance, such as anadditive or modifying agent, to be introduced in a liquid carrier, thecarrier being rapidly absorbed into the granules. Although the granuleshave a high degree of porosity, the coherence between the microcrystalspermits even an aqueous carrier to be absorbed into the capillarynetwork of the granule to achieve a substantial impregnation of thegranule without changing its form. Further, the absorption of water orother carrier from the surface of the granules as applied takes place sorapidly that the ordinary tendency of a granular sugar product to cake,pack or agglomerate when wet can be readily controlled by simpleagitation and intermixing of the granules.

In one method of practicing the present invention, the SDA granules,which are free-flowing and porous, are formed into a bed, such as a bedor mass of granules in a suitable mixing apparatus. A liquid dispersionof the additive or modifying agent is sprayed or otherwise distributedon the bed of the sugar granules while agitating and intermixing thebed. The dispersion can be applied at a rate facilitating rapidabsorption of the dispersion from the outer surfaces of the granulesinto the interiors thereof, and the agitation and intermixing iscontrolled to prevent caking or packing, the granules remaining discreteand free-flowing without intergranule agglomeration occurring to anyappreciable extent.

When the impregnation of the granules has been completed, they can befurther processed in various ways, as will be disclosed in the followingdetailed specification. It will be understood that these additionalsteps form a part of certain preferred embodiments of the presentinvention.

DETAILED DESCRIPTION Where the granular starting material has beenprepared by the process of the cited copending application Ser. No.674,168, the material will comprise generally spherical granules ofcrystalline sugar, and the granules will be formed essentially ofaggregates of microcrystals of the sugar, such as microcrystals ofdextrose monohydrate, microcrystals of sucrose, etc. The averagegranular size can range from to 400 microns, such as an average sizeabout of 200-300 microns. This granular size can be varied by screeningand/or milling or crushing the granular product, but exact granulesizing is not essential for the purposes of the present precess.

The granular starting material will usually contain less than 1 percentfree moisture, and preferably less than 0.5 percent by weight freemoisture. While granular products containing free moisture as high as 2or 3 percent can be used, such higher moisture contents tend to limitthe obtainable impregnation at least in the initial cycle, and thereforeit is preferred to utilize a starting material which contains little orno free water.

As used in the present application, the terms Spray-Drier Aggregated" orSDA" mean sugar granules originating from individual spray-drieddroplets of a sugar massecuite comprising microcrystals of sugardispersed in a water solution thereof, additional microcrystals of thesugar having been deposited internally by removal of free water from theresidual solution after the spraying of the droplets. in terms ofphysical structure, the SDA granules comprise cohered sugarmicrocrystals with internal capillary networks. Sugar granules of thesame basic structure which are usable for the purpose of the presentinvention can also be produced by the process of copending applicationSer. No. 744,958 filed on even date herewith, and entitled SugarGranulation Process and Products Produced Thereby." In that process apumpable massecuite consisting of sugar microcrystals, such as dextroseor sucrose microcrystals suspended in a saturated solution of the sugaris intermixed with a bed of previously processed recirculated granularsugar, which is in the form of porous aggregated microcrystals. Themixture is then dried under conditions which contribute to the furthercrystallization of the sugar in solution as well as to water removal.The final product has the form of porous aggregates of cohered sugarmicrocrystals with internal capillary networks. If desired the particlesize can be varied by crushing or grinding and sieving. The fracturedgranules may not be spherical and will have a somewhat more irregularshape than SDA granules, but they are still free-flowing absorbentgranules, and can be used in the process of the present invention.Consequently, the terms Massecuite Aggregated Microcrystalline Sugar orMams granules, as used herein are intended to encompass such materials,which are generally equivalent in structural properties to the SDAgranules obtained by the process of the cited application Ser. No.674,168.

Where the MAMS granules are formed from total sugar, the DE. (dextroseequivalent) of the total sugar forming the granules is preferably atleast 88. MAMS total sugar granules having a DE. ranging from 92 to 98are desirable. However, total sugar granules can be produced having aDE. higher than 98 by a more complete conversion of the starchhydrolysate to dextrose. Therefore, if it is desired to employ MAMSgranules which are substantially pure dextrose, the starting materialfor the MAMS granules can consist of a pumpable massecuite composedsubstantially entirely of microcrystals of dextrose dispersed in a watersolution of dextrose. This massecuite can be Spray-Drier Aggregated orotherwise formed into MAMS granules, as described above. Similarly, MAMSgranules can be formed from other cyrstallizable sugars, such assucrose, fructose, maltose, lactose, xylose, mannitol, etc.

As used herein the tenn aqueous carrier" is intended to refer to wateror a mixture of water with a minor proportion (viz less than 50 percent)of another solvent, where the mixture still functions essentially as anaqueous carrier, that is, any additional solvent has not so modified thesolvent properties of the water that the aqueous carrier is no longer agood solvent for crystalline sugar. The terms liquid medium" or "liquidcarrier" are intended to refer to both aqueous and organic solventcarrier, as well as mixtures thereof. As used herein, the terms organicsolvent medium" or "organic solvent carrier" are intended to refer to aliquid carrier formed from a single organic solvent or a mixture oforganic solvents which may either be substantially anhydrous, or maycontain a minor proportion (viz less than 50 percent by volume) ofwater.

A preferred solvent for the purpose of the present invention is waterunmixed with any other solvent. However, it may be desirable to employsmall amounts of an organic solvent, such as ethanol, as an aid to thedispersion of the additive or modifying agent in the water carrier. Theaqueous or organic solvent carrier preferably contains the impregnatingagent in a true solution. However, if the additive is normally a liquidnot miscible with the carrier, it can be emulsified with the carrier, orimpregnated directly where the volume to be added and viscosity do notpresent ditficulties.

In some cases, a finely divided (colloidal) solid can be suspended inthe liquid carrier and at least partially impregnated into the granulesas the carrier is absorbed. Consequently, the term dispersed" ordispersion" is used herein to refer to the incorporation of a modifierin the carrier by forming a true solution, as well as a suspension of acolloidal solid material, or an emulsion dispersion.

in many applications of the present invention, the referred to herein asan impregnating additive, additive or modifying agent will consist of anedible material, since the resulting product will be eaten, or at leasttaken internally, as in the case of medicine. However, the presentinvention is not limited to edible applications, since the MAMS granulescan serve as a carrier for a wide variety of substances, where the useof the final product may be dictated by the properties of the additive,which may or may not be edible. Among the various kinds of substanceswhich can be incorporated in the sugar granules by the use of an aqueouscarrier are synthetic sweetening agents, edible organic acids, and foodflavoring substances. In addition, colors and perfumes can beincorporated, as well as sugars unlike the base sugar of the granules.By way of specific example, a concentrated fruit juice comprising anaqueous solution of sugars, flavoring substances, and color bodies, canbe combined with the MAMS granules to produce a powder from which afruit juice drink can be prepared. Flavoring oils can be incorporated asan oilin-water emulsion, or an alcohol extract, such as the vanillaextract, can be dispersed into the aqueous carrier.

Certain organic impregnating agents, which are normally liquid, or whichcan be heated and applied as a liquid, can be used as their own solvent.However, in typical applications, a nontoxic organic solvent-solubleimpregnating agent will be dissolved in a suitable organic solvent, andapplied to the MAMS granules, preferably by spraying onto the granuleswhile they are being agitated. Among the various kinds of substanceswhich can be incorporated in the sugar granules by use of an organicsolvent carrier are food flavoring substances, such as those commonlyprepared as alcohol tinctures or extracts, colors. and perfumes. By wayof specific example, a food flavoring substance, such as vanilla extractor lemon oil, can be employed to impregnate the granules.

The present invention can also be used for modifying the sweetnessproperties of the sugar forming the MAMS granules. For example, aconcentrated water solution of a relatively sweet sugar, such assucrose, invert sugar, or fructose, can be used to impregnate dextrosegranules to thereby increase the total sweetness of the product. By aseries of impregnation cycles, as will subsequently be described, from 5to 20 percent of a supplemental sugar can be added in this way. Othersugar properties which can be provided by mixed sugars with one basesugar predominating can be readily produced by the method of thisinvention.

In certain applications, the MAMS granules can function as a carrier forthe added substance. For example, a water dispersion of a medicinalagent can be incorporated in the granules. In this way, sticky or evennormally liquid medicinal agents can be prepared in a dry granular form.The resulting granules can be filled into capsules, or they are alsoadapted for tableting, as described in copending application Ser. No.744,645 filed on even date herewith, entitled Tablets and Method ofForming. Where a flavoring agent is desired in the tablets, this can beincorporated along with the medicinal agents, and the resulting granulesformed in the tablets by compression, as described in the above citedapplication. The impregnated granules can also be used to fonn candyrings or cough drops by a similar tableting or compression process. Forexample, a flavor such as oil of Wintergreen or oil of peppermint can beemulsified in an aqueous carrier, the carrier impregnated in thegranules, and thereafter the granules formed by compression into candylozenges. Preferably, as will subsequently be described, the impregnatedgranules are dried to remove the water before being formed into thetablets or lozenges. This procedure is advantageous when the modifyingagent is relatively nonvolatile compared to water.

When practicing the method of the present invention, it is advantageousto spray the liquid dispersion of the modifying agent onto a bed of theMAMS granules while agitating and intermixing the bed. However, othermethods of application can be used. Tumble-type mixing equipment can beemployed, such as a rotary mixer with internal mixing flights. Anattrition-type mixer may also be advantageous. Desirably, the agitationand intennixing of the granular bed should be suffrcient to effectivelyprevent packing or caking of the granules during spraying. The bed canbe observed during the spraying operation and if any tendency to pack orcake is observed, the speed or amount of mixing can be increased.Agglomeration of the granules should not occur. Preferably, theimpregnated product has approximately the same average particle size asthe granular starting material.

Because of the capillary networks of the granules which extend fromtheir outer surfaces to the interior thereof, the liquid carrier duringthe applications is rapidly absorbed from the surface of the granules.Apparently this prevents the exterior surfaces of the granules frombecoming sticky, which would promote caking or agglomeration. Thediscovery that this does not occur can be explained on the basis thatcapillary attraction sucks the applied liquid into the interior of thegranules with great rapidity, the removal of the liquid from the surfaceof the granules being substantially as rapid as it is applied. Thus, itis only necessary to control the rate of spraying within reasonablelimits to achieve the desired impregnation without packing oragglomeration. The permissible rate of spraying is of course related tothe amount of mixing, the volume of the bed, and the nature of thematerial being sprayed. In a particular application, the condition ofthe granules as the spray is applied can be observed, and if anysubstantial accumulation of liquid on the surface of the granules isnoted, the rate of spraying can be decreased until substantiallyinstantaneous absorption is obtained. In extreme cases an ageing orcuring period may be desirable to allow further penetration and theattainment of a uniform liquid distribution.

The upper limit on the amount of spray which can be applied in oneabsorption cycle is the point at which the granules begin to pack orcake, becoming non-free-flowing and unmanageable in the mixingapparatus. This will usually be higher for organic solvents than forwater.

In using an aqueous carrier, it will generally be preferred to keep thefree water content (not including water of crystallization) of thegranules below 5 percent by weight. Starting with MAMS granulescontaining substantially no free water (less than 0.5 percent), asuitable operating range is from I percent up to 4 percent free waterfor each impregnation cycle. If it is desired to incorporate more of thecarrier for the purpose of increasing the content of the modifier, thiscan be done by repeated cycles. For example, the granules after thecompletion of the spraying step can be subjected to drying to reduce thewater content, such as to a water content of less than 1 percent byweight free water, and then again subjected to a spraying operation, andso on until the desired level of the modifier is achieved. The totalinternal volume available for impregnation, that is the free volume ofthe capillary network itself, has not yet been determined with accuracy,but is appears to be substantially greater than the volume which wouldbe occupied by adding 5 percent free water by weight.

The procedure of drying the granules after the impregnation ispreferably employed where the modifying agent is substantiallynonvolatile relative to water, as would be the case when the modifyingagent is normally a solid, or where it is a relatively nonvolatileliquid. The drying procedure itself is not critical, and can be carriedout in ordinary drying equipment for granular materials, such as a gasfired rotary dryer. As indicated previously, where the base sugar is ina crystal form which can be changed by overdrying, it may be preferredto terminate the drying with a small residual content of free moisture,such as 0.5 to 1 percent free water by weight. For example, MAMSgranules composed substantially entirely of dextrose monohydrate andhaving a moisture content of approximately 0.5 percent by weight can beimpregnated with a water carrier up to a free moisture content of atleast 4 percent by weight, then subsequently dried back to a .moisturecontent of 0.5 percent by weight, and the cycle repeated as often asnecessary until the desired content of the modifier is incorporated.

MAMS granules composed of alpha dextrose monohydrate will contain about8 to 9 percent by weight water of crystallization. By drying undersuitable conditions part or all of the water of crystallization can bedriven off to form anhydrous alpha dextrose, or a mixture of monohydrateand anhydrous dextrose, without disrupting the granular structure. Suchgranules can be used where it is desired to add more than 4 to 5 percentwater per impregnation cycle. For example, if the dextrose granulescontain from O to 6 percent water of crystallization, the total amountwhich can be added is increased to the range of 8 to 14 percent. Part ofthe added water will be taken up as water of crystallization. Anhydrousor partially anhydrous alpha dextrose MAMS granules are also moreabsorptive for organic solvents, permitting a larger amount to beimpregnated per cycle. In general, as much as 10 to l2 percent by weightof an organic solvent carrier can be applied without causing packing orcaking of the granules.

Depending on the application to be made of the impregnated granules,various organic solvents can be used. However, for food or medicalapplications, a nontoxic, edible organic solvent is desirable, such asethanol, glycerol, propylene glycol, or mixtures of such solvents. Forexample, a mixture of ethanol and propylene glycol can be used as animpregnating solvent.

After completing the impregnation, part or all of the carrier solventmay be removed by evaporation: As an alternative to drying the granulesafter impregnation, the impregnated granules can be packaged in suitablesealed containers, which are capable of substantially preventing theevaporation of the solvent. Even if the granules are substantially fullysaturated with the solvent, it has been found that the granules remainfree-flowing when packaged in this manner, and the loss of volatilesubstances can be avoided. This procedure is particularly suitable foradding volatile essences, such as flavoring oils, to the MAMS granules.

In another procedure, the impregnated granules are subjected to a secondtreatment in which a pore closure material is applied. For example, thepore closure material can comprise a vegetable oil or fat, or ahydrocarbon or synthetic wax. The coating material can be sprayed on tothe granules while they continue to be agitated and intermixed in thesame apparatus as used for the spray mixing, the application of thecoating material being continued at least until the coating on theexterior surface of the granules closes the outer ends of the capillarypassages. Among the other water-insoluble materials which can be usedare shellac, rosin, and paraffin. Where desired, the coating materialcan be dissolved in or thinned with a volatile organic solvent, and thesolvent evaporated as the coating is formed. The coating can beeffective where it substantially retards the release or loss of theimpregnated substance and/or carrier solvent by reduction of porosity ofthe surface layers.

The coating material can be soluble or dispersible in water, and appliedas an aqueous solution or dispersion. For example, water solutions ordispersions of vegetable gums can be used. including Agar, Carrogeenan,Alginates, Guar Gum.

Gum Acacia and Gum Tragacanth, gelatin, pectin, starches and dextrins,malto-dextrin and like polysaccharides, carboxymethyl cellulose andsodium caseinate. Other pore closure materials include methyl cellulose,polyethylene glycols, hydroxypropylcellulose, polyvinyl pyrrolidone,ethyl cellulose and zein. Most of these coating materials can be appliedas aqueous solutions or dispersions, although some of the materials canbe used in a mixed water and organic solvent solution. For example, zeincan be dissolved in a mixture of water and ethanol or water andisopropanol, and applied as a coating material.

Certain porosity reducing materials can be applied in the liquid phaseand then allowed to harden. These include paraffins and hydrogenatedtriglyceride fats. For example, normally solid hydrogenated vegetableoils can be heated and applied as a liquid, and then cooled on thesurface of the granules to form a sealing layer. In still anotherprocedure, a water solution of a crystallizable sugar, such as aconcentrated sugar syrup is applied, and the sugar is crystallizedwithin the capillary passages of the granules. This reduces porosityalthough complete scaling is not usually obtained.

In a desirable embodiment of the present invention, the MAMS granulesare prepared from a starch hydrolysate composed of dextrose andoligosaccharides and having a DB. of at least 94 up to about 98. Forthis material, the basic granule structure is primarily microcrystallinealpha dextrose monohydrate with oligosaccharides, being in the form of asolid solution. Although the oligosaccharides comprise only a fewpercent of the total sugar content of the granules, the solid solutionapparently acts as an auxiliary binder or cementing agent, and therebyassists in maintaining the structural integrity of the granules duringthe processing step of the method of this application. In otherembodiments, however, it will be understood that the MAMS granules canbe formed substantially entirely of dextrose, such as dextrose granuleshaving a D.E. of 98.0 or higher, or the granules can be formed of othersugars, such as sucrose, fructose, maltose, lactose, xylose, mannitol,etc.

This invention is further illustrated by the following numbered examplesin which the starting material (unless otherwise stated) is Spray-DrierAggregated granules prepared as described in copending application Ser.No. 674,168. The granules are composed of alpha dextrose monohydratecrystals with a few percent of oligosaccharides. The DB. of the granulesis about 95-96, and they contain approximately 9.0 percent water byweight, less than 0.5 percent being free water. The SDA Sucrose of theexamples is also prepared by the process of said application Ser. No.674,168.

EXAMPLE I The absorptive property of the SDA Total Sugar granules isillustrated by the following:

a. 3600 g. of SDA Total Sugar granules (9 percent water content) wasplaced in a laboratory Twin Shell Blender (Model LB-2990 ofPatterson-Kelly Mfg. Co., Stroudsburg, Pa.) equipped with a combinationliquid feed and intensifier bar. Four 100 ml. portions l27 g. each) of ared mixed fruit juice concentrate (60 percent D.S.) were added with a 20minute mixing period (intensifier bar disengaged) following eachaddition. The product may have a damp appearance but it was not stickyand its flow properties were such that it could be readily transferredor otherwise handled. After an additional 2-hour aging period it becamedry to the touch and completely freeflowing. [t dried readily onexposure to the air to give a readily soluble product suitable as afruit juice drink when mixed with water. A microscopic examinationshowed the fruit juice solids to be distributed uniformly throughout theinterior of the granules.

b. In a test for comparative purposes, 3600 g. of crystalline hydrateddextrose was place in the blender and 100 ml. increments of the juiceconcentrate were added as above.

After the first l00 ml. addition the sugar had a wet appearance and itsfree-flowing nature was noticeably reduced. After the second 100 ml.addition the sugar became so wet it stuck to the blender walls and wasso non-free-flowing that it could not be effectively mixed. The test wasterminated and the contents had to be largely removed by hand from theblender. It was difiicult to handle and dry and the dried product waslumpy and hygroscopic. The added fruit juice solids was entirely on thecrystal surfaces.

EXAMPLE 2 The absorbtive properties of the SDA granules is illustratedby the following example in which their behavior is compared with thatof conventional crystalline dextrose when intennixed with propyleneglycol which was selected as representative of a nonvolatile fluidadditive. A solution of ethanol and propylene glycol having a 2:] volumeratio was prepared and colored with a red dye to facilitate migrationstudies.

a. To 8 pounds of SDA total sugar granules in a laboratory model TwinShell Blender (Model LB-2990 of Patterson Kelly Mfg. Co.) equipped witha combination liquid feed and intensifier bar was added I00 ml.increments of the above alcohol-glycol mixture. After each addition theblender was operated for lO-l 5 minutes with the intensifier bardisengaged. No change was noted in the freeflowing properties of themixture until the fifth addition (500 ml.) when it became slightly lessfree-flowing and started to show signs of agglomeration. After theseventh addition (700 ml.--approx. 14.6 percent weight gain of solutionor 6.2 percent weight gain of propylene glycol) the mass appeared dampbut, even after ageing in a closed container, remained quitefree-flowing. On removal of the alcohol by air drying, its free-flowingproperties improved and the granules were uniformly colored by the dye.

b. The above procedure was repeated using ordinary crystalline dextrosein place of the SDA sugar granules. The first 100 ml. addition of thealcohol-glycol mixture resulted in a marked reduction of thefree-flowing properties of the sugar. The second 100 ml. additionreduced it even more so that the mass appeared very damp and tumbleden-masse. After the sixth 100 ml. addition the mass was unworkable andhad to be removed from the blender by hand. When aged in closedcontainers it appeared wet and adhered to the container walls. When airdried the material tended to cake and migration of the nonvolatilepropylene oxide was observed in each case as evidenced by the formationof nonuniform colored layers in the samples.

EXAMPLE 3 One part of calcium cyclamate and six parts of citric acid isdissolved in six parts of an aqueous imitation raspberry flavor. Themixture is then thoroughly mixed into parts of an SDA total sugar. Thedamp mixture is then dried in a circulating air stream to give auniform, nonagglomerated, free-flowing granular product. Two teaspoonsof the material will dissolve readily when stirred in a glass of waterto produce a pleasant flavored beverage.

EXAMPLE 4 Ten parts of twofold orange oil (containing 0.02 percent BHTstabilizer) is mixed with 0.1 part emulsifier (Tween-20) and the mixtureis emulsified on 20 parts of water. The emulsion is then uniformlydistributed on 400 parts of SDA total sugar granules which have beenvacuum oven dried to a total moisture content of 1.5 percent. Theemulsion will be absorbed almost immediately, giving a free-flowing dryproduct suitable as an orange flavored dusting sugar for bakery goods orconfectionery.

The orange flavored sugar of example 4 is placed in the bowl of a Hobartblender and to it was slowly added with medium agitation a solution of24 g. of malto-dextrin in 36 g. of water (made by heating them togetherand cooling to 80 F.) The material may acquire a damp feel, but shouldnot be sticky and should be readily transported and handled withoutdifficulty. After air drying it will resume its original completelyfree-flowing, readily soluble nature. The malto-dextrin will partiallyseal the surface openings of the granules so that the orange oil in thegranule interiors has a decreased tendency to volatilize or oxidize. lnexamples 4 and 5, the drying necessary after impregnation and coating isminimized due to the fact that the water added was removed, in part, inconverting the anhydrous dextrose to the hydrated form.

EXAMPLE 6 Twenty parts of gum arabic is suspended in 40 parts of waterand heated with agitation to give a viscous, uniform mixture which isthen cooled. Twenty parts of twofold cold pressed, stabilized orange oilis then added to the vegetable gum solution and emulsified with vigorousagitation. The emulsion is then distributed on and intermixed with 400parts of SDA total sugar granules which had been partially dehydrated byheating (2 percent total moisture). The resulting damp mixture isslightly agglomerated, but can be readily handled and when air driedwill give a free-flowing product, the granules of which will be somewhatlarger than those of the original SDA granules. They are readilysoluble, have a good flavor stability, and are suitable as a dryflavoring ingredient in beverage powders, cake mixes, etc.

EXAMPLE 7 Four hundred parts of SDA total sugar granules which have beenpreviously dried to a total moisture content of 2.0 percent areimpregnated with one part of oil of cinnamon using an alcohol solutionthereof. The mixture is intimately mixed with 108 parts of a 66 percentsolution of sucrose in water. The added water will be rapidly absorbedin converting the anhydrous dextrose to the hydrated form and themixture will soon attain a dry appearance and a free-flowing nature. Ona dry basis it can contain about 16.5 percent sucrose, which will notonly contribute to the sweetness of the product, but, by partiallyobstructing the surface openings of the individual SDA granules willminimize the loss on ageing of the volatile constituents of the oil. Theproduct produced is suitable as a cinnamon flavored sugar for use inbaked goods, on toast, etc.

EXAMPLE 8 Twenty parts of citric acid is dissolved in parts of anaqueous cherry flavor which is then uniformly distributed on andthoroughly mixed into 400 parts of SDA total sugar. The resultingmixture may have a damp feel, but can be handled and conveyed, etc.without difficulty. lt is readily air dried to give a free-flowinggranular product with about 9 to 9.2 percent total water content. Asolution of 40 parts sucrose in 20 parts water is then distributed onand intermixed with this product to again give a damp, easily handledmaterial which again is readily dried to give a free-flowing granularproduct. A second addition of sucrose solution is similarly made and theproduct dried as before to give a free-flowing, readily soluble granularproduct suitable as a beverage base. The approximately l6 percentsucrose content contributes to the sweetness of the product and itslocation predominately on the granule surfaces has an inhibiting effecton the volatilization of the flavor components.

EXAMPLE 9 To partially dehydrated SDA total sugar granules (containing amixture of anhydrous and hydrated dextrose) having a total water contentof 4.0 percent is added to 5.5 parts of a dilute solution ofphenobarbital sodium. After thorough mixing, the water added is absorbedin converting the anhydrous dextrose to the hydrated fonn and theresulting granules will be free-flowing and uniformly impregnated withthe additive. No additional drying is necessary. The product is suitablefor use in filling unit dosage gelatin capsules. Depending upon thesugar quantity used per capsule, the strength of the original solutioncan be varied to give the unit medicine dosage desired.

EXAMPLE 10 Equal parts of single-fold California lemon oil and ethylalcohol are thoroughly mixed so that the oil is partially dissolved andpartially emulsified. The mixture is then added to 18 parts of SDA totalsugar (partially anhydrous with a total water content of 2 percent) andthoroughly mixed in a Hobart mixer during which process the alcoholpartially evaporated. The product will be completely free-flowing, havea dry appearance and feel, and will be readily soluble. It is suitableas a flavored sugar for use as a food additive.

EXAMPLE 1 1 Ten parts of a starch dextrin is cooked in 15 parts ofwater. The paste is cooled to F. and then thoroughly blended into 100parts of the lemon oil impregnated sugar prepared in example 10 above,and the mixture is air dried. The free-flowing product is readilysoluble and the dextrin deposited primarily on the surface and in thesurface openings of the granules will inhibit the oxidation andvolatilization of the flavor ingredients.

EXAMPLE 12 One part of single-fold vanilla extract (40 percent ethanol)is distributed on and thoroughly mixed into nine parts of SDA totalsugar which had been dried to the partially anhydrous state (total watercontent 4.0 percent). The water in the extract is absorbed in convertingthe anhydrous dextrose to the hydrated form and the mixture will beuniformly impregnated and free-flowing. It is suitable as a vanillasugar for use in foods.

EXAMPLE l3 To 8 pounds of vanilla sugar (prepared by the process ofexample 12 above) in the Patterson Kelly Twin Shell Blender is added 50ml. increments of a hydrogenated vegetable oil (m.p. 100 F., density0.88 g./ml.) which has been liquefied by heating to F. The addition isby means of the liquid feed bar and agitation is continued for 10-15minutes after each addition with the intensifier bar disengaged. The oilsolidified after penetrating the granules.

After five incremental additions (approx. 6.0 percent oil added on thesugar basis) the mixture will be still free-flowing enough to handle andconvey without difficulty. The oil film will be distributed uniformly onthe granule surfaces, and is effective in inhibiting the loss of flavorfrom the impregnant on ageing.

EXAMPLE 14 One part of oil of cinnamon bark is dissolved in 20 parts ofethanol and uniformly distributed on and intennixed with 400 parts ofSDA sucrose having a total moisture content of about 0.2 percent. Theresulting mixture will have a dry appearance, be completelyfree-flowing, and be readily water soluble. It is suitable as aflavoring material in the preparation of confectionery and other foodsand as a flavored sugar for use in baked goods, cinnamon-toast, etc.

EXAMPLE 15 The suitability of the SDA granules as a carrier for avariety of pharmaceutical or industrial additives is illustrated by thefollowing: four parts of l-menthol is dissolved in three parts ofethanol and the solution is distributed on and thoroughly intermixedwith a bed of nine parts of SDA total sugar granules having a totalmoisture content of about 9.1 percent. The alcohol is then removed byevaporation in an air stream. The product will contain 10 percentmenthol uniformly distributed through the granules and will be readilywater-soluble and completely free-flowing.

Many uses of the method and products of this invention will be apparent.Emulsions of oils (fruit, perfume, expectorant, spice, and oleoresin)for use as stable condiments and flavorings, air fresheners, dry coughmedicines, and other medicinals impregnated into the MAMS granulesshould have commercial value. A particular case is in the area ofmedicinals where the taste of the medicament is unpleasant, or where itis desired that the medicament be ingested in the intestinal or stomachwalls. In the latter case, the impregnated sugar can so function, whencoated with an enteric substance to give a sustained release medicament.Water solutions of acids, bases, salts, water-soluble medicinals, fooddyes, flavors, artificial sweeteners and sugars, etc., can be used asimpregnating agents to impart to the sugar a host of specializedapplications in the areas of food (imitation fruit drinks, dryconfectionery mixes, frosting) and medicinals (anti-acid tablets, oralvaccines) as well as other food and nonfood areas. The area of alcoholsoluble materials encompasses a wide range of commercially desirableitems which could be made more convenient by impregnating variousmaterials into the SDA or MAMS granules. Incorporation of dyes,perfumes, flavor extracts, elixirs and other alcohol solublemedicaments, spice oils, olcoresins, etc. into the porousmicrocrystalline aggregates will give rise to a wide variety of usefulproducts. Free-flowing textile dyes prepared by this method couldeliminate the mess of thy usual liquid or finely powdered dyes;impregnation of perfumes could result in a sustained release airfreshener; impregnation of cordial or liquer flavors could be useful indry cocktail mixes; and impregnation of fruit flavor and essences, meatflavors, spice oils and oleoresins could be used in the making andprocessing of cakes, cookies, puddings, frosting, gravies, soups, etc.

While in the foregoing specification this invention has been describedin relation to certain preferred embodiments thereof, and many detailshave been set forth for purpose of illustration rather than limitation,it will be appreciated that the method of this invention is applicableto additional embodiments than those described herein, and that many ofthe details set forth in the specification can be varied considerablywithout departing from the basic principles of the invention.

We claim:

1. The method of preparing an intimate mixture of starch hydrolysatesugar with an impregnating additive, comprising providing a free-flowingbed of granules composed essentially of cohered dextrose microcrystalsand oligosaccharides in solid solution, said granules being porous withinternal capillary networks, having been aggregated from amicrocrystalline massecuite of a starch hydrolysate total sugar with aD5. of at least 92 percent, the granules of said bed initially having afree water content of less than 1 percent by weight, applying to saidbed an aqueous carrier containing an impregnating additive, whileagitating and intermixing the granules of said bed to promote theabsorption of said carrier by said granules, said bed being maintainedin essentially free-flowing condition during said absorption, andterminating the application of said carrier before said granules containas much as 5 percent free water by weight.

substantially entirely of water and said granules at the beginning ofsaid application contain from 0 to 6 percent by weight water ofcrystallization in the dextrose hydrate portion of said microcrystals,said granules on the completion of said application having the dextrosemicrocrystals thereof substantially entirely in their hydrated form andcontaining not over 4 percent by weight free water.

5. The method of claim 1 in which said carrier is composed substantiallyentirely of water and said granules at the beginning of said applicationcontain not over 8 to 9 percent by weight water, said granules on thecompletion of said application containing at least 4 to 5 percent addedwater.

6. The method of claim 1 wherein said granules after absorption of saidcarrier are treated with a sealing material, said sealing material beingefi'ective to at least partially close the outer ends of said capillarypassages.

7. The product produced by the method of claim 6.

8. The method of claim 1 wherein said impregnating additive is awater-soluble normally solid substance, and said granules afterabsorption of said carrier are subjected to drying to remove water whileleaving said additive within said granules.

9. The product produced by the method of claim 8.

10. The method of claim 8 wherein after said drying step the granulesthus obtained are subjected to at least one additional cycle, includinga carrier application step and a drying step.

1 l. The method of preparing an intimate mixture of starch hydrolysatesugar with an impregnating additive, comprising providing a free-flowingbed of granules composed essentially of. cohered dextrose microcrystalsand oligosaccharides in solid solution, said granules being porous withinternal capillary networks, having been aggregated from amicrocrystalline massecuite of a starch hydrolysate total sugar withD.E. of at least 92 percent, the granules of said bed initially having afree water content of less than 1 percent by weight, applying to saidbed a nontoxic edible organic solvent carrier containing an impregnatingadditive, while agitating and intermixing the granules of said bed topromote the absorption of said carrier by said granules, said bed beingmaintained in essentially freeflowing condition during said absorption,and the application of said carrier being terminated before saidgranules begin to pack or cake.

12. The method of claim 11 wherein said granules after absorption ofsaid carrier are treated with a sealing material, said sealing materialbeing effective to at least partially close the outer ends of saidcapillary passages.

13. The method of claim 11 in which the dextrose microcrystals of saidgranules at the beginning of said application are at least partially inanhydrous form.

#4. The methodof claim 11 wherein said impregnating additive is anormally solid substance dissolved in said carrier, arid said granulesafter absorption of said carrier are subjected t drying'to remove saidcarrier while leaving said additive within said granules.

15. The method of claim 14 wherein after said drying step the granulesthus obtained are subjected to at least one additional cycle, includinga carrier application step and a drying step.

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2. The method of claim 1 in which the dextrose microcrystals of saidgranules at the beginning of said application are at least partially inanhydrous form.
 3. The method of claim 1 in which said granules at thebeginning of said application contain from 0 to 6 percent by weightwater of crystallization.
 4. The method of claim 1 in which said carrieris composed substantially entirely of water and said granules at thebeginning of said application contain fRom 0 to 6 percent by weightwater of crystallization in the dextrose hydrate portion of saidmicrocrystals, said granules on the completion of said applicationhaving the dextrose microcrystals thereof substantially entirely intheir hydrated form and containing not over 4 percent by weight freewater.
 5. The method of claim 1 in which said carrier is composedsubstantially entirely of water and said granules at the beginning ofsaid application contain not over 8 to 9 percent by weight water, saidgranules on the completion of said application containing at least 4 to5 percent added water.
 6. The method of claim 1 wherein said granulesafter absorption of said carrier are treated with a sealing material,said sealing material being effective to at least partially close theouter ends of said capillary passages.
 7. The product produced by themethod of claim
 6. 8. The method of claim 1 wherein said impregnatingadditive is a water-soluble normally solid substance, and said granulesafter absorption of said carrier are subjected to drying to remove waterwhile leaving said additive within said granules.
 9. The productproduced by the method of claim
 8. 10. The method of claim 8 whereinafter said drying step the granules thus obtained are subjected to atleast one additional cycle, including a carrier application step and adrying step.
 11. The method of preparing an intimate mixture of starchhydrolysate sugar with an impregnating additive, comprising providing afree-flowing bed of granules composed essentially of cohered dextrosemicrocrystals and oligosaccharides in solid solution, said granulesbeing porous with internal capillary networks, having been aggregatedfrom a microcrystalline massecuite of a starch hydrolysate Total Sugarwith D.E. of at least 92 percent, the granules of said bed initiallyhaving a free water content of less than 1 percent by weight, applyingto said bed a non-toxic edible organic solvent carrier containing animpregnating additive, while agitating and intermixing the granules ofsaid bed to promote the absorption of said carrier by said granules,said bed being maintained in essentially free-flowing condition duringsaid absorption, and the application of said carrier being terminatedbefore said granules begin to pack or cake.
 12. The method of claim 11wherein said granules after absorption of said carrier are treated witha sealing material, said sealing material being effective to at leastpartially close the outer ends of said capillary passages.
 13. Themethod of claim 11 in which the dextrose microcrystals of said granulesat the beginning of said application are at least partially in anhydrousform.
 14. The method of claim 11 wherein said impregnating additive is anormally solid substance dissolved in said carrier, and said granulesafter absorption of said carrier are subjected to drying to remove saidcarrier while leaving said additive within said granules.
 15. The methodof claim 14 wherein after said drying step the granules thus obtainedare subjected to at least one additional cycle, including a carrierapplication step and a drying step.